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CHEMICAL PROBLEMS 2019 no. 4 (17) ISSN 2221-8688
UDC 541.49 + 546.562
COMPLEXES OF METALS WITH DIHYDRAZONES OF SUCCINIC ACID
DIHYDRAZIDE
P.A. Fatullayeva
Institute of Catalysis and Inorganic Chemistry name of .M.Nagiyev 113, G.Javidave.,AZ 1143 Baku, Azerbaijan; e-mail:pfatullayeva@,mail.ru
Received 10.09.2019
Abstract: Bis-(3,5-di-tert-butyl-salicylidene) dihydrazone of succinic acid dihydrazide was synthesized and its analogue-reduced azomethine bond. The complexes of Mn (II) and Fe (II) with these ligands were obtained. Based on the data of IR-, electron spectroscopy and elemental analysis, of the obtained complexes is assumed the binuclear structure. The possibility of catalytic reduction of the azomethine bond with NaBH4 to the corresponding succinic acid bis-(2-hydroxybenzyl) succinic dihydrazide was shown. It was found that all obtained compounds have high bactericidal and fungicidal activities.
Keywords: hydrazides, succinic acid hydrazones, Mn(II), Fe(II) complexes. DOI: 10.32737/2221-8688-2019-4-558-564
Introduction
Complexes of metals with salicylidene dihydrazones succin acid dihydrazide exhibit catalytic activity in the oxidation reaction of alkenes [1], are able to bind to DNA [2], and possess antimicrobial activity [3]. Salicyliden
dihydrazone dihydrazide succinic acid, like dihydrazone derivatives of other dibasic acids, is potentially hexadentate and 4 anionic, due to deprotonation of two phenolic hydroxyls and two enolic groups, as in structure E.
t-Bu
^OH
\ /
-CH^NWC\H2-CH2^ n/"^CH
HH
HO
^CH-
t-Bu
/ t-Bu
K
\ /
t-Bu
t-Bu
OH
\ /
—CH^N\ SC\ /C. ,N^>CH_
CH N" CH2—CHj CH
/ t-Bu
w
O
O
t-Bu
H
t-Bu
E
Therefore, this ligand is capable to form complexes of various compositions and structures. To date, binuclear copper (II) complexes [4], binuclear Fe(III) complexes [2], heterobinuclear complexes Zn(II), Cu(II), and Ni(II), [5,7] and binuclear complexes Mo(IV) [8] are known. Bi- and tetra-nuclear helicate compounds Eu (III) [9], helicate clusters of lanthanides and the influence of anions on their configuration [10] and dimeric
and polymer complexes of Sn [11] were also obtained.
Obtaining new complexes of dihydrazones of this series is of interest from the point of view of search of compounds with biological activity, in particular, antimicrobial and fungicidal. In this case, metal complexes with hydrazones reduced on the azomethine group can be of considerable interest.
CHEMICAL PROBLEMS 2019 no. 4 (17)
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Earlier, we studied complexes with schiff bases hydrogenated at the azomethine group obtained from salicylic acid hydrazide and 3,5-ditretbutyl salicylic aldehyde [12].In this work, we synthesized and studied
complexes of manganese and iron with dihydrazone derivatives of succinic acid dihydrazide and sterically hindered salicyl aldehyde-3,5-ditret-butyl salicylic and its reduced analog.
Experimental part
Obtaining bis(salicylidene) dihydrazone succinic acid dihydrazide(L1).
Succinic acid dihydrazide was prepared by boiling succinic acid diethyl ether and a 60% aqueous solution of hydrazine for 5 hours. Mp = 1800C. The Schiff base, bis(3,5-di-tretbuthyl-salicyliden)dihydrazone succinic acid L1, was obtained by condensation of 1 mole of succinic acid dihydrazide and 2 moles of 3,5-ditretbuthyl salicylic aldehyde in alcohol solution at the boil for 1 hour. After recrystallization from ethanol Mp> 2500 C. For C34H88N4O4
Calculated,%: C 66.23; H 14.29; N 9.09; O 10.39.
Found,%: C 66.20; H14.25; N, 9.12; O 10.37. Obtaining a complex of Mn(II) with the ligand L1.
10-3mol (0.616 g) of the ligand dissolved in 30 ml of ethanol was mixed with a methanol solution of 10-3mol (0.245 g) of Mn (CH3COOV4H2O. The solution turned brown. It was heated to a boil and allowed to crystallize. After 15 minutes, small brown crystals precipitated, which were separated and washed with ethanol. After drying in vacuum Mp> 2500C. For C68H172O8N8Mn2
Calculated:C 61.00; H 12.86; O 9.57; N, 8.37; Mn 8.21.
Found: C 60.99; H 12.85; O 9.58; N, 8.36; Mn 8.20.
Obtaining of Fe(II) complex with ligand L1.
10-3mol (0.616 g) of the ligand dissolved in 40 ml of ethanol was mixed with a methanol solution of 10-3mol (0.392 g) of Mohr's salt in 5 ml of water. Through for half an hour, the solution was filtered off and after prolonged standing dark gray crystals gradually precipitated. Mp> 2500C.For C68H172N8OgFe2 Calculated: C 60.90; H 12.84; N, 8.36; O 9.55; Fe 8.36.
Found: C 60.92; H 12.81; N, 8.34; O
9.56; Fe 8.37.
Reduction of bis(3,5-di-tretbuthyl-salicyliden)dihydrazone succinic acid (L2).
6.16 g (10-2mol) of Schiffs base and 0.2 g of PdCl2 were suspended in 40 ml of methanol, and NaBH4 (1 g) was added in small portions (until bleaching) with vigorous stirring. After adding the entire amount of borohydride, stirring was continued for another 0.5 hours. The solution was filtered, diluted with three times the amount of water and acidified with a 10% aqueous HCl solution to pH ~ 7. The precipitated substance was separated on a porous filter, washed with water, recrystallized from ethanol-water (1: 1), and dried in air. Mp> 2500C. For C34H92N4O4
Calculated: C 65.81; H 14.84; N, 9.03; O 10.32.
Found: C 66.09; H 14.52; N, 9.10; O 10.32. 22 The Mn2(L )2 and Fe2(L )2 complexes were
obtained by a similar procedure for Mn2(L1)2 12 and Fe2(L )2, by the interaction of the L
ligand with the Mn(CH3COO^4H2O salts and
the Mohr salt.
For C68H180N8O8Mn2
Calculated: C 60.63; H 13.37; N, 8.32; O 9.51; Mn 8.16.
Found: C 60.64; H 13.38; N, 8.31;O 9.50; Mn 8.17.
For C68H180N8O8Fe2
Calculated: C 60.53; H 13.35; N, 8.31; O 9.50; Fe 8.31.
Found: C 60.52; H 13.37; N, 8.29; O 9.48; Fe 8.32.
The antimicrobial activity of the investigated compounds was studied by the zonal diffusion method according to GOST 9.085-78. Mixtures of pure bacteria and fungi were taken for research.
Bacteria: - Mycobacteriumlacticolium-VKMB - 365, Pseudomonas aeruginosa
VKMV - 588 and Staphylococcus aureus. Pénicillium Cyclone - VKM-109;
The following fungal cultures were used to test Cladosporium - Geosmin - VKM - 1701. fungal activity: Aspergillusniger VKM-1119,
The discussion of the results
(3,5-ditretbutyl salicyliden)
dihydrazone of succinic acid dihydrazide L1, unlike other derivatives of salicylic aldehyde dihydrazones, is readily soluble in various organic solvents, including lowpolar ones. An attempt to directly hydrogenate the double azomethine bond in dihydrazone L1 with sodium borohydride is unsuccessfully and
insignificant amounts of the reduced ligand are observed in the reaction products, despite the fact that Schiff bases of various amines and aldehydes are usually easily converted to secondary amines by the action of NaBH4 in alcohol and other solutions. Therefore, we carried out catalytic reduction using palladium chloride as a catalyst.
t-Bu_^H O o HO /BU
_ ,ch2ch20n^ChO NaBH4
t-Bu ^"BU ethanole, 250C
L1
* TD _ ^ t-BU
t-Bu ^-vw-w — ~
W^ H 0 0 H H°=/
-CH2^ NfCsCH-CH2cN N^CH2 '
/
t-BU
H 2 H
L2
t-BU
Fig.1. Electronic absorption spectra in solutions of ethyl alcohol: 1-dihydrazone succinic
1 2
acid with 3,5-ditretbutyl salicylic aldehyde L , 2-reduced dihydrazone L .
Figure 1 shows electronic absorption spectra. The electronic spectrum L1 in the ultraviolet region contains n-n * absorption band at 285 nm due to the aromatic ring and n-n * in the azomethine group C = N at 330 nm.
2
In the reduced dihydrazone L the band at 330nm disappears due to the reduction of the double bond C = N andn - n *band of the aromatic ring is observed at 275 nm (Fig. 1).
The electronic spectrum of the absorption complex in the visible region contains absorption bands at 430 nm and 560 nm.
When dihydrazone L1 is complexed
with Mn(II), the band of the amide carbonyl group observed at 1640-1660 cm- 1 (in the starting ligand) disappears and the band of the azomethine group is shifted from 1620 cm -1 to 1605 cm -1.
Fig.2. IR absorption spectra: 1-dihydrazone succinic acid L1, 2- IR spectrum
of the complex with Mn2(L1)2.
There received data point to participation in the coordination of both of these groups, and the amide group coordinates the metal ion in enol form. The phenolic band OH, located in the initial ligand at 3440 cm-1, strongly decreases in intensity (~ 2 times) upon complexation. Thus, the Mn(II) ion is
coordinated with the ligand through the oxygen atom of the amide group in the enol form and the nitrogen atom of the azomethine group.
Elemental analysis indicates a metal ligand ratio of 1:1.
t-Bu
t-Bu
t-Bu—
OH
—CH=N
rCH2)2
yMi
-O O
t-Bu—^S-C^^ /C ^ ^
N (CH2)2 N OH
OH
J=CH -t-Bu
t-Bu
t-Bu
The Fe(II) complex with this ligand has the similar structure, the electronic and IR spectra of which coincide with the manganese complex.
We have studied the bactericidal and fungicidal properties of the synthesized compounds. As you know, lubricating oils during storage in conditions (elevated temperatures and humidity) are exposed to microorganisms action, that alter the
composition of the oils, increasing their acidity, and accordingly, corrosion ability.
To suppress the possibility of bacterial growth, additives in the form of pure chemical compounds or mixtures that have bactericidal properties are introduced into lubricating oils.
Currently, a large number of chemical compounds of various classes with bactericidal properties are known. However, metal complexes with reduced ligands have not yet
been studied as antimicrobial and fungicidal preparations. This section presents the test results of Schiff and reduced Schiff bases, their complexes with metals.
As can be seen from the table, all tested compounds have antimicrobial and antifungal activity. Among the tested compounds.
Among the compound, the Fe(II) complex with reduced succinic acid dihydrazone was most active.
It should be noted that high activity remains with decrease in the concentration of the substance (see table).
12 Table. Antimicrobial properties of dihydrazone succinic acid L , reduced dihydrazone L and
their complexes.
Zone diameter, Inhibition
sm
№ Conc. % Chemical formula Bacterium Fungi in CA
in MPA (meat medium (wort
peptide agar) agar)
1 2.0-2.2 1.0-1.2
1 0.5 L1 1.6-1.8 0.8-1.0
0.25 1.4-1.4 + +
1.0 2.2.-2.4 1.2-1.4
2 0.5 Mn2(L1)2 1.8-2.0 1.0-0.9
0.25 1.4-1.6 0.9-1.0
1.0 2.3-2.5 2.0-2.4
3 0.5 L2 1.9-2.0 1.4-1.6
0.25 1.6-1.8 1.0-1.4
1.0 2.7-2.8 2.2-2.6
4 0.5 Fe2(L2)2 2.0-2.6 1.6-1.8
0.25 1.8-1.9 1.4-1.5
+ - lack of activity
Thus, in this work, it was shown that bis (3,5-ditretbutylsalicylidene) dihydrazone of succinic acid dihydrazide (L1), its reduced
analog (L2) forms binuclear complexes of the
2 12
composition M (L )2 with ions Mn(II) and Fe(II) ), in which the coordination of the
ligand with the metal ion occurs through the oxygen of the carbonyl group, which is in enol form and the nitrogen atom of the azomethine group. It was found that all obtained compounds have high bactericidal and fungicidal activities.
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KdHRdBA TUR§USUNUN DiHiDRAZiDiNiN DiHiDRAZONLARI iLd METAL
KOMPLEKSLdRI
P. A Fatullayeva
AMEA akademikM.Nagiyev adina Kataliz vd Qeyri-uzvi kimya institutu AZ1143 Baku, H.Javid pr.,113, e-mail: [email protected]
Kdhrdba tur§usunun dihidrazidi ild bis-(3,5-ditretbutilsalisiliden) dihidrazonu vd onun azometin rabitdsi uzrd reduksiya olunmu§ analoqu alinmi§, onlarin Mn(II) vd Fe(II) kompleksldri sintez olunmu§dur. iQ-spektroskopiya, elektron spektroskopiya, element analizi ndticdldrind dsasdn alinmi§ kompleksldrin ikinuvdli oldugu mudyydn olunmu§dur. Gostdrilmi§dir ki, azometin rabitdsinin NaBH4-ld katalitik reduksiyasi yolu ild kdhrdba tur§usunun bis-(2-hidroksibenzil)dihidrazonunun alinmasi mumkundur. Mudyydn olunmu§dur ki, alinmi§ birld§mdldr antimikrob vd funqisid aktivliyd malikdirldr. Agar sozfor: hidrazidldr, kdhrdba tur§usunun hidrazonlari, Mn(II), Fe(II) kompleksldri.
КОМПЛЕКСЫ МЕТАЛЛОВ С ДИГИДРАЗОНАМИ ДИГИДРАЗИДА
ЯНТАРНОЙ КИСЛОТЫ
П.А Фатуллаева
Институт Катализа и Неорганической химии им.ак.М. Нагиева
Национальной АН Азербайджана AZ1143 Baku, пр. Г.Джавида, 113, e-mail:[email protected]
Синтезирован бис-(3,5-ди-третбутил-салицилиден)дигидразон и его аналог, восстановленный по азометиновой связи. Были получены комплексы Mn(II) и Fe(II) с этими лигандами. На основе данных ИК, электронной спектроскопии и элементного анализа предложено биядерное строение полученных комплексов. Показана возможность каталитического восстановления азометиновой связи с помощью NaBH4 в соответствующий бис-(2-гидроксибензил) дигидразид янтарной кислоты. Было обнаружено, что все полученные соединения обладают высокой бактерицидной и фунгицидной активностью.
Ключевые слова: гидразиды, гидразоны янтарной кислоты, комплексы Mn(II), Fe(II
